Metallizable azo dyes prepared from amino-benzothiazole derivatives and beta-naphthol derivatives



AMINO-BENZOTHI-AZOIEE"'DERIVATIWES AND fi-NAPHTHOL DERIVA IWES James M; Str'aley andY-John GiqFish'eiykKingsport Teiim, assignors to- E3Sfll13fl K0dfik Gompany Rochester, l-N. Y-., a corporationof-NewJersey I Thiswinventionarelates' to cerZtain: metalliz'able azoayes and to=theirmetallized complexesv I The non-metallized; dyes within. the scope: ofs this I invention-:haveithe striuctural for'mul-az amine having the structural formula:

. N X \CNH2 Y The resulting diazo compgund-isgthen reacted or coupled witha B-naphthol derivative having the structural formulai r are set forth in the specific examples and the procedures described in those exampleslrepre'sent methods by which the diazotiz ation reaction can be carried out.- The nonmetallized dyes, after their ,preparat'iomare reacted with a metal salt, such as suitable salts of nickel, cobalt, copper, chromium, manganese, iron or vanadium. The nonmetallized azo compounds can be metallized either on-or (iii the materials they color. Metallization can be carried out, for example, by treating the non-metallized azo compound with a solution or dispersion o'f the :metallizing agent. Although the metalcomplex is often formed at room temperature, we prefer to accelerate the process by heating-,susually with steam, for a short period of time. known to those skilled in the art to which this invention is directed;

Illustrative of the meta llizin'g agents that can be employed' are the halides, the sulfates, the acetates, the cyanides and the thiocyanates of nickel, cobalt, chromium, manganesetiron andvanadium as well as various copper compounds. Thus,nickelcliloride, nickel bromide, nickel sulfate, nickel acetate, nickel cyanide, nickle formate,

' nickelthiocyanate [N-i(SCN) l,,cobaltou's bromide, cobalti'c" chloride, cobal'tous' chloride, co'baltous acetate, co-

"[Fe (S'CN) ferric thiocyanate [Fe SCN and vanadiuinfthioeyanate [V(=SCN) areillustrat'ive of theme'tal- Iiz'ing agents that can be employed;

The non-metallized monoazo compounds described herein are useful for the dyeing of cellulose a'lkyl carvboxy li'c acid esters having 2 to 4 carbon atoms in the acid groups thereof, nylon, sulfone polyesters, polyethylene terephthalate and .polyarylonitrile. After applica'- tionto these materials, usually in the form of textile ma.-

'terials, the dye is metallized thereon.' The metallized azo ter'ia'ls such as wool, silk, nylon and acryl-onitrilepolw a 'd z area defined inthe formula set forth above fertile-dyes "of this invention. "One method of carryingout'thefiiazot-i tton' re ction involves dissolving the-aminocompound in ana' nfeous hydrochloric acid 'solutionand 'thenadding sodium nitrite I 'The" details. pf' the diagdtization" reaction mers, for example, Coloration can also 'beefiecfedby incorporating the non-metallized or metallized azo compounds into the spinning dope, spinning the fiber as usual and converting the non-metallized azo compbun'ds to their metallized form. alsowhe metallizing agent can be incorporated in the spinning dope, the fiber spun as usual and then dyed with the non-metallized'monoa'z'o compoundsto .formthe metal complex on the fiber. The

new metallized dyes ofour invention are preferably formed by heating the vnon-r'netallized azo dye with the metallizing agent .in .organicsolvents such as, for example, cellulose acetate, cellulose acetate-propionate, acrylonitrile polymers, polyamides, methyl cellosolve and formamide.

- As=iswell kn-own, one of 'thedis'a'clvantages dyed :cellu lose acetate textile fabrics sufier in comparison with some of the dyed competing textile fabrics, such as cotton, wool and viscose, for example, islack of fastness to washing. Many schemes have been proposed to remedy this situationfbut all suffer from some significant vfault. By meansof-our invention dyed cellulose acetate textile ma- The metaIli-zation is efiected by procedures well a and gas are obtainable. These results may be obtained by dyeing the cellulose acetate textile material with the non-metallized azo compounds and then treating the dyed cellulose acetate textile material with suitable metal salts which cause the original dye to form metallic complexes which are resistant, for example, to the action of washing, light and gas. These results can also obtained by incorporating the metallized azo dye into the cellulose acetate spinning dope and spinning the fiber as usual. Thus, by means of the present invention. the disadvantage noted above with respect to the wash'fastness of dyed cellulose acetate textile materials is either entirely or largely overcome. Cellulose acetate has been particuarly referred to because it is the most widely used cellulose alkyl carboxylic acid ester.

When the metal complex is formed on a cellulose alkyl carboxylic acid ester, such as cellulose acetate fiber, the use of a metal thiocyanate appears to be advantageous and is preferred. Nickel thiocyanate appears to be especially useful and particular claim is laid to its use. Next to nickel thiocyanate the use of cobalt thiocyanate is preferred.

Metallization will be described in detail with reference to nickel and cobalt inasmuch as the metallized dyes containing these materials in complex combination appear to be advantageous. However, it will be clearly understood that the non-metallized azo compounds can be metallized with the other metals disclosed herein. The azo compounds disclosed herein have varying utility as dyes. The degree of utility varies, for example, depending upon the material being colored and the actual dye employed.

The following examples are illustrativeof this invention.

Example 1 A solution of 1.9 g. sodium nitrite in 12.5 cc. of concentrated H SO were prepared at 70 C. To this solution there was added with good stirring 25 cc. of mixed propionic-acetic acid (1:5), hereinafter referred to as 1:5 acid. The mix was brought to C. and 4.55 g. (0.025 mole) of 2-amino-6-methoxy-benzothiazole were added, maintaining the temperature below C. cc.

of 1:5 acid were added at this temperature and the mix stirred 2 hours further. The diazo thus prepared was added to a solution of 7.8 g. of N,N-di-fi-hydroxyethyl- 2-naphthol-6-sulfonamide in 80 cc. of 1:5 acid at 5 C. After minutes the mineral acid was neutralized to Congo red with ammonium acetate and the coupling allowed to proceed at l020 C. for 2 hours. The dye was then precipitated by drowning in about 1500 cc. of cold water. The product was filtered off, washed with water and dried in vacuo at 60 C. The yield was 10.5 g. of product having the formula:

N OH

ornonzon SOzN CHzCHzOH and dyeing polyacrylonitrile fiber in blue shades of good light fastness.

Example 2 2-amino-6-methoxybenzothiazole was diazotize d as in Example 1. The coupler in-Example 1 was replaced by 8.2 g. of N,N-di-;3-cyanoethyl-2-naphthol-6-sulfonamide.

According to the procedure of Example 1, there; was. ob tained 12.8 g; of product having the formula:

and which dyes polyacrylonitrile fiber in blue shades of good fastness to the action of light.

Example 3 The products of Examples 1 and 2 on cellulose acetate produce reddish-orange shades of poor fastness to the action of light or laundering agents. The dyeings so obtained were padded with a- 2% solution of nickel thiocyanate under such conditions that the pickup is 60l00% on the weight of the goods. The dried cloth was steamed 10 minutes at 5 p. s. i., rinsed 10 minutes at F. in a solution of 0.5% Na CO and 0.5 soap, rinsed and dried. "The resulting deep, bright. blue fabrics showed nobreak after 20 hours exposure on;

the fadeometer, whereas the original dyeing broke badly after only 5 hours. Furthermore, the fabrics withstand-i with no alteration, a standard AATCC wash test at. 160 F. with soap and soda ash.

Example 4 A solution of 5.7 g. (0.025 mole) of 2-amino-6-methylsulfonylbenzothiazole in g. of 50% H SO was cooled to 0 C. and treated with a solution'of 2.1 g. NaNO in 12.5 (is. concentrated H 50 below 5 C. The diazo solution was stirred 2.5 hours at this temperature and run into a solution of 8.3 g. (0.025 mole) of 2-naphthol- 6-sulfomorpholide in cc. of 1:5 acid at 0-5" C. The mineral acid was neutralized to Congo with ammonium acetate and stirred 2 hours longer without cooling. The product was drowned in 2000 cc. water and isolated by filtering, washing and drying at 60 C. The yield was 8.8 g. of a'solid having the formula:

and dyeing polyacrylonitrile fiber in violet shades.

Example 5 0.500 g. of the product of Example 4 was ground intimately with 2 g. of a 10% solution of sodium lignin sulfonate. This was mixed with 5 g. of di-fi-hydroxyethylsulfide and then with 50g. of a 6% gum tragacanth solution. After complete dispersion, 30 g. of a solution containing 8 g. of ammonium thiocyanate and 4 g. of nickelous chloride crystals was stirred in. A cellulose acetate cloth was printed on a roller print machine with the so-obtained paste, dried, and aged 10 minutes at 5 p. s. i. steam pressure The fabric was soaped at 120 F. with a solution of 0.5 soap and 0.5% Na CO After rinsing with hot water and drying there wasobtaineda-fabric bearing deep violet patterns on .a clear white ground. The print had excellent re- 'sistance to the action of light or laundering agents.

5 *Ifli--foll6wing table lists additional examples of dye's 'witnam: scope ;of:' this invention showing tlre: colors ioftth'e non-metalli'zedand metallized dyes.

6 Efampl'd li" ThecoupleninExample,1-wastreplacedlbyjeg. E2- naphtholI-fi-isulfonamide.-1 The. resulting. .,dye impartarto g Color SubstiIutedm-Ammm s (loupletiUsed Metalbenzothiazole. r .Used. p I

' 'Or'lginaI' Final fl-Methoxy N,N Di a hydroxyethyl e hydroxynaphthalene 2-sulfonamide.

D0: .fi-Hydroxynaphthalenem-sulfomorpholide. t

Do: iN-Mthyl 6 hydroxy naphthalene 2 sulldnamida.

Do .N,N' Di B hydroxyethyl 7 -,hydroxynaphthalene f l-sultdnamide: D0 N -B Mgthoxyethyl 7 hydroxynaphthalene- 1 sulnam e. N:- fl. r-Hydroxyethyi 6 hydroxynaphthalene 2 sulfonamid v v N,N Di 'eyanoethyl -'6"- hydroxynaphthalene 2 sullonamide. 4 7-Hydroxynaphthalene-2 suliomorpho1ide Do "N Ethyl N -.hydroxyethyl 6 hydroxy naphthalene-Zsulfonamide. V Do -N-Glyceryl-6-hydroxya1aphthalene-Zsulfonamrde N Methyl N carboxy= methyl 6 hydroxy naphthalene-2-sulfonamide.

N 5 Hydroxypropyl 6 hydmXynaphthaIeHQI-QZ sulfonamide.

N Trimethylolmethyl 6 hydroxynaphthalene 2 sulfonamide Example 6 TIie -annne of Example 2 was replaced by 2-amino-5- methoxybenothiazole. The resulting gdye .imparted orange shades to cellulose acetate whicl1- upon treatment with,

cellulose acetate orange shades and, after treatment with nickel thio'cyanate. theiresulting dye producesdeep. blue colors-"of excellent fastness'to' light and washingr Example 12 The:aminei-inzExampleLhwas replaced? by 5 g..of 2- aminoz-fii-methylthiobenzothiaZole:. After treatment: with v nickelxthiocyana'te; the. resu1ting1dye'impartsla blues color 2-naphthol-6-sulfonamide in?- 160.-cc. ofv1.:5l acidnat 5 C. The mix was neutralized after.20 minutes and worked up as in Example 1. The product yielded orange shades on cellulose. acetater'which were transformed to bluish violet of excellent fastness properties by treatment with"nickeltthiocyanate.

Example 8 The amine in Examplel was replaced by 5.6 g. of 2- amino-6-fi-methoxyethoxybenzothiazole and: the coupler by 7.7 g. of N-B,'y-dihydroxypropyl-2 naphthol-6-sulfonamide.- The-resulting dye is a blue-violet shade after treatment "with nickel thiocyan-ate.

Example 10 The;.aminez.ini. Examplei.2: was replacedfbyr4;5r g. of 2- .aminoi4;6-dimethylbenzothiazole; The? resulting: dye, .aftemtreatment :with' nickel thiocyanate; produces clear bluersh'ades; oirexcellentifastness on: cellulose acetate;

to' celluloseiacetatefabrics. Example 13* The amine in Example 11 was replaced by 5.25 g. of 2- amino-6-thiocyanobenzothiazole. The resulting dye,

after treatment.- with nickel thiocyanate; imparts a blueviolet color to cellulose acetate.

Example 14 9.9 of'2-amino-6-nitrobenzothiazole were diazotized as in Example 7and then coupled with 15 g. of N-fimethoxyethyI-Z-naphthol-6-sulfonamide, as in Example 7. Theresulting. dye, after.- treatment, with nickellthiocyanate, produces aviolet coloron cellulose acetate.

Eicample' 15" Theamine inExample ;7 was replacedbyv g. 0552. amino-.6-fl-hydroxyethylbenzothiazole; Theresultingfldy'e imparts a blue color. of excellent. fastness to, cellulose acetate, after treatment.with..nickel thiocyanate.

In'the preparationof couplersfor the practice of this ethyl-2-naphthol-6-su1fonamide, melting at 157.5-9 C,

' cleus.

In like manner the intermediates in the following table were prepared, In the first column is shown the position of the sulfonamide group on, the naphthalene nu- In the second column is shown the configuration of the sulfonamido group. In the third column the melting point of the coupler product is recorded. The OH group is always in the 2 position of these couplers.

Position Configuration Melting Point S O; N(CH1CH@OH)2 122.53 O. S OzNHCH2CH2OCH3 102-4 0.

S OQNHOHZCHZOH 157.54) C 02 C s 166-63 C. S O2N(CH2CH2CN)3 l8486 C.

CH2-CH2 S OzN 206-8 G CHz-CH:

8 S 021N132 18890 C. 6 -S O3NHCH1CH2OCH3 105-7 G.

6 S OzN l01-5 C.

CHzCHaOH 6 S OzNCHgCHOHCHzOH 185200 C.

S O N CHzCHzOlh Oil. S OzNHO(CH2OH)a Oil.

CH3 S O N Dee. 280 0.

. OHzCYOOH 6 S OQNHCHaCHOHOHa 1558 C.

CHaCH-r S zN\ 0 218-9 0.

CHgCHt S OzNHCHiCHzOH Oil. S O2N(CH1CH2OH)2 164.5-6 O.

We claim:

1. As a composition of matter, the azo compounds selected from the group consisting of monoazo compounds and their metal complexes containing. a metal selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium, said monoazo compounds having the structural formula:

' R1 SOZN wherein X and Y are selected from the group consisting of hydrogen, bromine, nitro, alkoxy, alkylsulfonyl, alkoxyalkoxy, thiocyano and monohydroxyalkyl, and R and R are selected from thegroup consisting of hydrogen, monohydroxyalkyl, alkyl, cyanoalkyl, alkoxyalkyl, thy-dihydroxypropyl, trimethylolmethyl, p-chloroethyl, carboxyalkyl and heterocyclic morpholide ring containing the amino nitrogen atom and R and R and wherein the terms alkyl and alkoxy refer to lower alkyl and lower alkoxy.

2. As a composition of matter, the azo compounds having the structural formula:

N OH

/R1 SOSN 8 wherein X and Y are selected from the group consisting of hydrogen, bromine, nitro, alkoxy, alkylsulfonyl, alkoxyalkoxy, thiocyano and monohydroxyalkyl, and R and R are selected from the group consisting of hydrogen, monohydroxyalkyl, alkyl, cyanoalkyl, alkoxyalkyl, Byy-dihydroxypropyl, trimethylolmethyl, B-chloroethyl, carboxyalkyl and a heterocyclic morpholide ring containing the amino nitrogen atom and R and R and wherein the terms alkyl and alkoxy refer to lower alkyl and lower alkoxy.

3. As a composition of matter, a complex metal compound containing a metal selected from the group consisting of chromium, cobalt, copper, iron, manganese, nickel and vanadium in complex combination with the monoazo compounds having the formula set forth in claim 2.

4. As a composition of matter, the azo compound having the structural formula:

\C-N=N CHsO- CHzCH OH SOQN CH2CHzOH 5. As a composition of matter, the azo compound having the structural formula:

\CN=N onto CHzCHzCN 6. As a composition of matter, the azo compound hav- CHZGHICN ing the structural formula:

\C-N=N C H3O I S 02N C HzC H: OH

7. As a composition of matter, the azo compound 8. As a composition of matter, the azo compound having the structural formula:

SOQN 9. As a composition of matter, the nickel complex of the azo compound having the formula set forth in claim 4.

10. As a composition of matter, the nickel complex of the azo compound having the formula setforth in claim 5.

11. As a composition of matter, the nickel complex of the azo compound having the formula set forth in claim 6.

12. As a composition of matter, the nickel complex of the azo compound having the formula set forth in claim 7.

13. As a composition of matter, the nickel complex of the azo compound having the formula set forth in claim 8.

References Cited in the file of this patent UNITED STATES PATENTS FOREIGN PATENTS Switzerland Sept. 29, 1956 

1. AS A COMPOSITION OF MATTER, THE AZO COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF MONOZAO COMPOUNDS AND THEIR METAL COMPLEXES CONTAINING A METAL SELECTED FROM THE GROUP CONSISTING OF CHROMIUM, COBALT, COPPER, IRON, MANGANESE, NICKEL AND VANADIUM, SAID MONOAZO COMPOUNDS HAVING THE STRUCTURAL FORMULA: 